Process and composition for rubberizing water repellent material and product thereof



Patented Feb. 28, 1933 PATENT orrlca mm C. TEAGUE, OF JACKSON HEIGHTS, NEW YORK, ASSIGNOB 1'0 GENEBAII' RUBBER COMPANY, OF NEW YORK, N. Y A CORPORATION OF NEW JERSEY PROCESS AND COMPOSITION FOR BU BBERIZING WZA'I'ER BEBE-LINN! MATERIAL AND rnonuc'r warms I 1T0 Drawing. Original application filed April 1, 1925, erlal No. 20,010. Divide'il'and this application filed August 18, 1927, Serial No. 218,966. Renewed August 5, 1982.

This invention relates to the manufacture of rubberized material and to new and improved compositions for such manufacture.

This apphcation is a division of my co- 5 pending application Serial No. 20,010, filed A ril 1. 1925.

t has been diflicult to apply rubber in dise1 persion either as rubber latex or as artificial aqueous dispersions of rubber directly to 1 materials which are re ellent to water, the

reason being that a satisfactory penetration is not obtained. This inventlon aims primarily to overcome this difiiculty and to facilitate the close contact of rubber in dis ersion with materials which are water repel ent or non-adsorptive by nature or as the result of some process, with an agent which wets the same, generically termed an organic polar compound or wetting agent. The invention 2 also aims to enable the rubber to be more or,

less uniformly applied to associations of such water repellent materials, such as crashed stone, concrete, pebbles, cork, wood, associations of fibres-which may be woven or knitted or stranded or simply matted or felted. It also aims to enable rubber to be applied with more or less rapidity depending upon the olar compound selected, whereby the rate of penetration can be controlled and to govern moreor less the quantity of rubber distributed as a binder in and on the desired materials. In the case of crushed stone, concrete, cork, arid similar non-fibrous water repellent materials, or materials not easily wet by water, the action of the polar compounds is believed to be that of facilitating the wetting. In the case'of fibrousmaterial, such as cotton, hemp, jute, manila fibre,, sisal, whether manufactured into articles or unas- 40 sociated, lack of the property of being wet ent, from the specification following, to one skilled in the art.

With the preferred embodiment in mind but without intention to limit its scope more than is required by the prior art, the" inventreating water repellent materials with a polar compound or wetting agent and a disersion of rubber, with or without vulcaniz- 1ng and/or filling ingredients as may be desired, the polar compounds being capable of application to the Water repellent material t er before or simultaneously with the aqueous dispersion of rubber. Preferably the polar compound is incorporated in the aqueous dispersion of rubber, (either natural or artificial) before application to the water repellent material. More specifically the invention relates to treating an association of fibres with a polar compound and a dispersion of rubber which may or may not contain vulcanizing and/or filling ingredients.

It has been found that a eat variety of agents designated generica 1y as organic lar com ounds may be employed as media or initial y wetting water repellent or nonabsorbent materials such as stone, concrete,

cork, fibres, such as cotton, hem wool, hair, asbestos in fact any mineral? animal or vegetable fibre which contains in or on its fibres oils, waxes or greases or other substances capable of preventing or retarding aqueous dispersions of rubber from enetrating or saturating the material. An some of these polar compounds are better suited for particular materials than are others. Hence it is to be understood at the outset that the invention is broad in scope and is not limited to the use of a particular polar compound as one or another may be selected to meet the requirements of the material to-be treated and to obtain the desired product.

According to the invention sulphonated 1 castor oil, sulphonated cotton seed oil, sulphonated olive oil, sulphonated arachis oil, ortho toluidine, sodium sulphanilite, sodium salicylate, thiourea, ammonium (linolenate and isolinolenate) saponin, sodium dioxynacphthalene disulphonate, potassium oleate, so

ium naphthalene sulphonate or other related, com unds having similar properties may each bi: employed as the wetting agent and applied to a water-repellent material or to any association thereof, either prelimi-r narily before the aqueous dispersion of rub- 50 tion may be briefly described as consisting in her or they may be and preferably are mixed with the aqueous dispersion of rubber.

' While the proportions or quantities of the polar compounds or wetting agents employed maybe varied, it has been found that 5 parts .on 100 parts of rubber generallg yield satisfactory results. The aqueous i rubber may ployed of course the rubberized material capacity for wettin should be subjected to suitable treatment for effecting vulcanization. The above-named polar compounds or wetting agents are merely given by way of illustration, there being many other substances having a similar water-repellent fibres at various speeds or time rates and facilitating the penetration therewith of aqueous dispersions of rubber and the ultimate binding together or coating of the water-repellent materials with the rubber. And all substances having such a capacit are intended to be comprehended within the road invention. While as before stated the polar compounds or wetting agents may be applied to the materials initially (before the latex or other aqueous dispersion of rubber), it is deemed more. desirable, as the invention is understood at present, to mix them with the aqueous dispersion of rubber and apply the mixture or composition to the materials in one operation.

It is believed that the mixture of the wet ting agents and rubber latex or other aqueous dispersion of rubber when applied to the water-repellent materials efliciently carries the rubber in and onto the materials because of an orientation of the the hy rocarbon portion a the moleculesfor the water-repellent materials. Apparently the organic polar compounds wet the materials andprepare the way for the ready ingress or contact of the aqueous dispersion of rubber. The water carrier of the particles of rubber follows the polar compound to or into the mass with greater or less rapidity depend ing upon the particular polar compound employed, and utimately results in a uniform coating or deposit of rubber in, on or among the materials.

The following empirical test indicates the speed or rapidit with which various organic olar compoun s penetrate an association of bres. A test of more or less arbitrary character was conducted by applying a mixture consisting of 5 grams of each of the polar compounds indicated and 100 grams of rubher in the form of latex containing molecules of the ,wettin agent and of the fgreater aflinity of solids. Two (2) cc. of each of the thus prepared compositions were accurately measured and placed on a given paper felt and the time required for this liquid to completely penetrate into and be absorbed by the felt was noted. The results were as follows:

100 rubber as latex: 5 sulphonated castor oil 0.75 5 ortho toluidine 3.2 5 sodium sulphanilite 4.5 5 sulphonated castor oil and 5 sodium salicylate 6 5 thiourea 7.75 5 sodium salicylate 9 5 ammonium linolenate and isolinolenate I 5 saponin 16 5 sodium dioxynaphthalene disulphonate 2 5 potassium oleate 25 5 sodium naphthalene sulphor. nate 58 (Alone) 60 5 sulphanilic acid 120 5 tannin 150 5 urea nitrate (GP) 150 Filling and/or vulcanizing ingredients and/or accelerators may be incorporated as thereof is governed or controlled by the deliberate incorporation of an agent or agents for wetting the materials and paving the way for an aqueous dispersion of rubber, with or without other ingredients, to pass more or less thereinto, and whether the penetrating agent be applied before or simultaneously with the rubber latex or its equivalents.

Of course the roduct of this invention may be additiona 1y treated with rubber or rubber substances according to known practices for various specific ends or purposes. For instance fibrous material treated according to this invention may have an additional skim coat applied thereto. Or an impregnated base material may have an additional body of rubber composition built thereupon.

As stated above, the invention is suitable for application to water repellent fibres or to associations of water repellent fibres. As a specific example of the application of the invention to jute rope cord or fabric, a compound such as 100 parts of rubber as latex vegetable fibres or wool or mixtures of these.

or an aqueous dispersion of rubber containing solids, 2 parts sulphonated castor oil and 50 parts gilders Whiting may be employed. The cord or rope is assed through the compound and then dried and polished. If desired the concentration of the rubber dispersion may be varied to give differing. amounts of rubber in the cord. The rate and extent of penetration depends upon the proportion of polar compound used and upon the time the rope is permitted to'stay in the rubber dispersion. The polar compound may be replaced by other materials such as are mentioned above. A jute cord of about diameter after impregnation showed an increase of about in tensile strength. Another similar cord showed approximately 18% improvement in tensile strength and approximately 76% improvement in resistance to wear.

The invention may be applied to carpet, such as the carpetmade from rags, grass,

It is often quite essential that penetration of the rubber dispersion takes place and to accomplish this polar compounds have given satisfactory results. A suitable composition is:

Parts 100 rubber as latex containing 12.5 solids 50 gilders whiting 20 sulphonated castor oil As indicated in the above formulae latex or dispersed rubber can be used in varying degrees of dilution. The sulphonated castor oil can be varied in amount or partially or completely replaced by other soluble oils or other penetrating agents such as indicated above. Compounding ingredients such as gilders whiting or other inert materials can be used in varying amounts. Stabilizing, thickening or hardening a cute such as for example sodium silicate, g ue, starch, dextrine, and the like may be used where desired. Coloring agents or vulcanizing ingredients may likewise be used in the dispersion and deposited in and/or on the carpet.

Cotton rope, cord, hose or belting may also be treated with rubber dispersions according to the present invention. Such associations of fibres may be mpregnated in their entirety or in the case of rope may have the central cord impregnated before the surrounding cords are braided on the central cord,.and a second impregnation given the outer braided portion. The same applies to belting. It is possible to obtain increases in resistance to flexing or abrasion amounting to as muchas 300%.by impregnating with a rubber dispersion containing a polar compound. Depending upon the thickness and ti 'htness of the cord or belting and upon the nature and amount of the polar compound, increases in abrasion resistance tion may be applied also to low grade aper stocks or paper stocks containing! fi rous or filling materials which are diflicult to penetrate with rubber dispersions. The use of a polar compound or wetting agent in the ru ber dispersion makes it possible to penetrate such paper stocks. As 5 ific instances, cheap paper felt may treated with the compositions set forth in this invention to form fioor'coverings. Hard calcndered and hi hly embossed or crinkled papers such as t ose used as bag'and barrel inings may be treated with rubber dispersions containing polar compounds yielding a hi hly satisfactory waterproof coating whic adheres very firmly to the paper surface due to the fact that it is in intimate contact with or has penetrated into the fibrous association. 7

These rubber dispersions, by var ing the polar agent used and by including ller materials when desirable, may also be employed as top sizing for paper and other sheet materials.

To illustrate the application of the polar compound to materials which are not necessarily penetrated, in which instance the polar compound acts more as a wetting agent, the application of rubber dispersions containing polar compounds to stone surfaces is mentioned. Ta ing for example a con. crete, the surface of which has not been finished with neat cement, a rubber dispersion containing a polar compound may be spread thereupon or otherwise placed in contact therewith and allowed to dry. It will be found that the rubber coating thus laid upon the concrete will have a much higher degree of adhesion to, the concrete than an ordinary rubber dispersion which does not contain a polar compound or wetting agent. The same holds true for crushed stone such as the granites, limestones, slags, and other stones or powdered materials whose surface is inclined to be granular. The adhesion of rubber compound to such granular surfaces increases directly with the degree of wetting.

Other non-fibrous water repellent materials may be similarly treated. For example cork and other such woody products, and even wood itself ma ber dispersions containing polar compounds, the result being that the rubber dispersion be treated with rubafter drying will be tightly adherent to the material by virtue of the fact that penetration and/or thorough wetting has taken place.

In the specification and claims the terms wetting agent or polar compound is emplo ed to comprehend those substances genera ly organic substances which possess a gradation of properties within the molecule different sections of which have appreciably different properties such as solubility, or

allinity for other substances and particularly 1 a capacity to wet water repellent materials.

These terms wetting agent or polar compound include those substances which show relatively low interfacial tension toward both water resistant materials on one hand and water on the other. In still other words, these terms include those substances each molecule of which is composed essentially of two parts, viz., a hydrocarbon, which has a strong attraction for and is miscible with oils, greases, and waxes, and which also is now been made practicalto manufacture commercially a wide variety of rubberized articles or materials having an association of water-repellent fillers: or fibres constituting the whole or a art thereof, and this invention is regard as basic in character. Reference should be 'made to the accompanying claims for an understanding of the scope of the invention.

The term water repellent material in the appended claims is intended to include those materials which are not readily wet by water or by an aqueous dispersion of rubber, such materials including concrete, wood, stone,

cork, and similar materials which have a granular surface or a greasy or oily surface which is not.readily wet by'water. In certain of the claims the term water repellent fibrous materials is employed to signify such cotton, hemp, jute, wool, asbestos, sisal, flax,

and other fibres which possess the characteristics of being water repellent to a varying degree. The term fibrous material is also meant to include those fibres and associations of fibres such as cords, ropes, felts, sheets, manufactured articles such as carpet, bagging, hose, belting, paper, cardboard, pressed articles made from ground wood fibres, and

in general all manufactured articles which of or wetting with water. I

Having thus described my invention, what I claim and desire to protect by Letters Patcut is:

1. A process for treating water repellent material which comprises preliminarily applying to said material a sulphonated organic polar compound, and then allowing rubber in the form of an aqueous dispersion of rubber to enter into intimate contact with said material.

2. A process for treating water repellent material which comprises preliminarily applying to said material a sulphonated organlc polar compound, and then allowing rubber in the form of an aqueous dispersion of rubber containing vulcanizing ingredients to enter into intimate contact with said material.

3. A process for treating water repeilent fibrous material which comprises preliminarily applying to said material a sulphonated or anic polar compound, and then allowing ru ber in the form of an a ueous dispersion of rubber to enter into intimate association with the fibres of said material.

4. A process for treating water repellent fibrous material which comprises preliminarily applying to said material a sulphonated organic polar compound, and then allowing ru ber in the form of an aqueous dispersion of rubber containing vulcanizing ingredients to enter into intimate association with the fibres of said material.

5. A process for treating water repellent material which comprises preliminarlly applying to said material sulphonated castor oil, and then allowin rubber in the form of an aqueous dispersion of rubber to enter into intimate contact with said material.

6. A process for treating water re ellent material which comprises preliminarily applying to said material sulphonated castor oil, and then allowing rubber in the form of an aqueous dispersion of rubber containing vulcanizing ingredients to enter into intimate contact with said material. I

7. A process for treating water repellent fibrous material which comprises preliminarily applying to said material sulphonated castor Oll, and then allowing rubber in the form of an aque0us dispersion of rubber to enter into intimate association with the fibres of said material.

8. A process for treating water repellent fibrous material which com rises preliminarily applying to said material sulphonated castor 011, and then allowing rubber in the form of an aqueous dispersion of rubber containing vulcanizing ingredients to enter into intimate association with the fibres of said material.

9. A process for rubberizing water repellent material which compriscs preliminarily treating said material with a wetting agent, treating said material with an aqueous dispersion of rubber, and drying.

10. A process for rubberizing water repellent material which comprises preliminarily treating said material with material from the group comprising sulphonated castor oil, sulphonated cotton seed oil, sulphonated olive oil, sulphonated arachis oil, ortho toluidine, sodium sulphanilite, thiourea, sodium salicylate, ammonium linolenate and isolinolenate, saponin, sodium dioxynaphthalene disulphonate, potassium oleate, and sodium naphthalene sulphonate, treating sai.d;material,

with an aqueous dispersion of rubber, and drying.

11. A process for rubberizing water repellent material which comprises preliminarily treating said material-with a sulphonated oil, treating said material with an aqueous dispersion of rubber, and drying. p

12. As an article of' manufacture, a water repellent fibrous material impregnated with material from the'group comprising sulphonated castor oil, sul honated cotton seed oil,

Signed at New York, county and State of New York, this 16 day of August, 1927 'MERWYN O. TEAGUE; 

